2,2-Bis(haloalkenyl)-1-substituted-1-dialkoxyphosphoroethylene fungicides

ABSTRACT

The 2,2-bis(haloalkenyl)-1-substituted-1-dialkoxyphosphoroethylene compounds of this invention are effective fungicides. In particular, some of the compounds of this invention are especially effective against Grape Downy Mildew.

BACKGROUND OF THE INVENTION

With the world more dependent for food on an ever decreasing amount ofcultivated land, it is necessary to develop fungicides which protectcrops from fungicidal destruction.

U.S. Pat. No. 3,761,596 discloses ethylbis(allylthio)methylidenemalonates and chloro analogs thereof asfungicidal.

U.S. Pat. No. 4,007,279 discloses 2,3-dicyano-5,6-dihydro-p-dithiin andits 5-alkyl derivatives as fungicidal.

SUMMARY OF THE INVENTION

The compounds of the present invention are represented by the formula:##STR1## wherein A.

R and R¹ are independently

1. lower alkenyl,

2. lower alkynyl,

3. lower alkenyl substituted with 1 to 3 of the same or differenthalogens, or

4. lower alkynyl substituted with 1 to B 3 of the same or differenthalogens;

B.

R² and R³ are independently

1. hydrogen or

2. lower alkyl;

C. R⁴ and R⁵ are independently lower alkyl;

D. R⁶ is

1. cyano, or ##STR2## wherein R⁷ is lower alkyl; and E.

Y is either

1. oxygen, or

2. sulfur.

Among other factors, the present invention is based on my finding thatthe compounds of this invention are effective fungicides. Additionally,some of the compounds of this invention are especially effective againstGrape Downy Mildew.

Due to their superior fungicidal activity, preferred R and R¹ groups arevinyl, vinyl substituted with 1 to 3 halogens, acetynyl, 2-butenyl,propargyl, and the like.

Particularly preferred R and R¹ groups include the vinyl groupssubstituted with 1 to 2 halo atoms.

Preferred halo groups are bromo and chloro.

Most preferably, R and R¹ are mono- and dichlorinated vinyl groups.

Preferably, R² and R³ are hydrogen.

Preferred R⁴ and R⁵ lower alkyl groups include, for instance, methyl,ethyl, n-propyl, isopropyl, and the like.

Most preferably R⁴ and R⁵ are both ethyl.

Preferred R⁶ groups are cyano and ##STR3## Most preferably R⁶ is cyano.

Preferred R⁷ lower alkyl groups include, for instance, methyl, ethyl,n-propyl, isopropyl, and the like.

Most preferably R⁷ is ethyl.

Most preferably Y is oxygen.

Definitions:

As used herein, the following terms have the following meanings, unlessexpressly stated to the contrary.

The term "alkyl" refers to both straight- and branched-chain alkylgroups. The term "lower alkyl" refers to both straight- andbranched-chain alkyl groups having a total of from 1 through 6 carbonatoms and includes primary, secondary, and tertiary alkyl groups.Typical lower alkyls include, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, t-butyl, n-hexyl, and the like.

The term "alkenyl" refers to unsaturated alkyl groups having a doublebond (e.g., CH₃ CH═CH(CH₂)₂ --,) and includes both straight- andbranched-chain alkenyl groups.

The term "lower alkenyl" groups refers to alkenyl groups having from 2through 6 carbon atoms. Typical lower alkenyl groups include, forexample, ethylene, but-3-enyl, hex-4-enyl, 2-methylpent-4-enyl, and thelike.

The term "alkynyl" refers to unsaturated alkyl groups having a triplebond (e.g., CH₃ C.tbd.C(CH₂)₂ --) and includes both straight- andbranched-chain alkynyl groups.

The term "lower alkynyl" refers to alkynyl groups having from 2 through6 carbon atoms and includes, for example, but-3-ynyl, hex-4-ynyl,3-methylpent-4-ynyl, and the like.

The term "halo" or "halogen atom" refers to the groups fluoro, chloro,bromo and iodo.

The term "thioallyl" refers to the group: ##STR4## with the conventionalnumbering system employed. Thus, the term "thio-3'-chloroallyl" refersto the group:

    --SCH.sub.2 CH═CHCl.

The term "alkoxy" refers to the group R¹⁰ O-- wherein R¹⁰ is alkyl.

The term "lower alkoxy" refers to alkoxy groups having 1 through 6carbon atoms and includes, for example, methoxy, ethoxy, t-butoxy,hexoxy, and the like.

The term "phosphoro" refers to the P→O group while the term"thiophosphoro" refers to the P→S group.

The term "dialkoxyphosphoro" refers to the ##STR5## and includes, forexample, ##STR6## and the like.

The term "dialkoxythiophosphoro" refers to the ##STR7## and includes,for example, dimethoxythiophosphoro, diethoxythiophosphoro, and thelike.

The term"1-cyano-1-diethoxyphosphoro-2-thioallyl-2-(thio-3'-chloroallyl)ethylene"refers to the group: ##STR8##

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention are prepared according to thefollowing synthetic scheme: ##STR9## wherein R, R¹, R², R³, R⁴, R⁵, R⁶and Y are as defined above and X is a halogen.

The compounds of Formula I wherein R and R¹ are identical to each otherand R² and R³ are identical to each other are conveniently prepared asshown in Reactions (1) and (2) above.

Reaction (1) is conveniently conducted by adding 2 to 2.5 equivalents ofan inorganic base to the appropriate reagent, II. The reaction is donein the liquid phase employing an inert organic solvent such as dioxane,tetrahydrofuran, diethyl ether, dichloromethane, and the like. Suitableinorganic bases include, for instance, potassium hydroxide, sodiumcarbonate, potassium carbonate, and the like. Preferably, the reactionemploys pulverized potassium hydroxide as the base in a dioxane medium.1 to 2.5 equivalents of carbon disulfide, IV, is then added to thesystem. The reaction is generally conducted at from 0° to 100° C.,although preferably at from 5° to 40° C. and is generally complete fromwithin 1 to 24 hours. Reaction pressure is not critical and forconvenience, the reaction is generally conducted at atmosphericpressure. The product, V, is then isolated by conventional proceduressuch as extraction, filtration, chromatography, distillation, oralternatively is used in Reaction (2) without purification and/orisolation.

Reaction (2) is conducted by adding 2.0 to 2.5 equivalents of theappropriate reagent, VI, to V. The reaction is conducted in the liquidphase employing an inert organic solvent such as dimethylformamide,toluene, methanol, and the like. Reaction pressure is not critical andfor convenience, the reaction is generally conducted at atmosphericpressure. The reaction is generally conducted at from -10° to 50° C.,although preferably at from 20° to 40° C. and is generally complete fromwithin 1 to 48 hours. The product, I, is isolated by conventionalprocedures such as extraction, filtration, chromatography, distillation,and the like.

The synthesis of compounds of this invention wherein R and R¹ are notidentical is depicted in Reactions (3), (4) and (5).

Reaction (3) is conveniently conducted by adding an essentiallyequimolar amount of an inorganic base to the appropriate reagent, II.The reaction is done in the liquid phase employing an inert organicsolvent such as dioxane, tetrahydrofuran, dimethylformamide, and thelike. Suitable inorganic bases include, for instance, potassiumhydroxide, sodium carbonate, potassium carbonate, and the like.Preferably, the reaction employs pulverized potassium hydroxide as thebase in a dimethylformamide medium. 1 to 2.5 equivalents of carbondisulfide, IV, is then added to the system. The reaction is generallyconducted at from -20° to 50° C., although preferably at from -5° to 20°C. and is generally complete from within 1 to 24 hours. Reactionpressure is not critical and for convenience, the reaction is generallyconducted at atmospheric pressure. The product, VII, is isolated byconventional procedures such as extraction, filtration, chromatography,distillation, and the like. Alternatively and preferably, the product,VII, is used directly in Reaction (4) using the same vessel and solvent.

Reaction (4) is conducted by adding an essentially equimolar amount ofthe appropriate reagent, VI, to VII. The reaction is conducted in theliquid phase employing an inert organic solvent such asdimethylformamide, dioxane, and the like. Preferably, the reactionsolution is the same as was employed in Reaction (3) with theappropriate reagent VI merely added to the system after completion ofReaction (3). Reaction pressure is not critical and for convenience, thereaction is generally conducted at atmospheric pressure. The reaction isgenerally conducted at from 0° to 100° C., although preferably at from15° to 25° C. and is generally complete from within 1 to 24 hours. Theproduct, VIII, is isolated by conventional procedures such asextraction, filtration, chromatography, distillation, and the like.Alternatively and preferably, the product, VIII, is used directly inReaction (5) using the same vessel and solvent.

Reaction (5) is conducted by adding an essentially equimolar amount ofan inorganic base to VIII. The reaction is conducted in the liquid phaseemploying an inert organic solvent such as dimethylformamide, dioxane,and the like. Preferably, the base is added at from 0° to 5° C. to thesame solution as was employed in Reaction (4) with the appropriate basemerely added to the cooled system after completion of Reaction (4).Suitable inorganic bases include, for instance, potassium hydroxide,sodium carbonate, potassium carbonate, and the like. Preferably, thereaction employs pulverized potassium hydroxide as the base. Afteraddition of the base, an essentially equimolar amount of the appropriatereagent, IX, is added. This reaction is generally conducted at from 0°to 100° C. and is generally complete from within 1 to 48 hours. Reactionpressure is not critical and for convenience, the reaction is generallyconducted at atmospheric pressure. The product, I, is then isolated byconventional procedures such as extraction, filtration, chromatography,distillation, and the like.

Reactions (1), (3) and (5) involve the addition of a solid base to anorganic solvent. In order to facilitate reaction completion, aphase-transfer catalyst is preferably employed in these reactions to aidin the transfer of the solid base into the organic solvent. Preferredcatalysts include, for instance, tetraalkylammonium halides. Aparticularly preferred catalyst is tetra-n-butylammonium bromide. Ingeneral, 0.025 equivalents of the catalyst have been found sufficient toaccomplish the catalytic effect desired.

Alternatively, if the base employed is in an aqueous solution, aphase-transfer catalyst is employed to facilitate transfer from theaqueous phase to the organic phase.

Reactions (2) and (4) involve adding a potassium thiolate to an organicmedium. Preferably, in order to speed the time required for reaction, acatalytic amount (˜0.025 equivalents) of a phase-transfer catalyst isadded. Catalysts such as tetraalkylammonium halide salts are preferred.

Utility:

The compounds of this invention are useful for controlling fungi.Additionally, some of the compounds are useful in controlling leafblights caused by such organisms as Phytophthora infestans conidia,Alternaria solani conidia, Septoria apii, downy mildew caused byorganisms such as Plasmopara viticola, and other fungal infectionscaused by organisms such as Piricularia oryzae and Erysiphe polygoni.

However, some fungicidal compounds of the invention may be morefungicidally active than others against particular fungi. Table II listsa summary of activity against some particular fungi for severalcompounds of this invention.

When used as fungicides, the compounds of the invention are applied infungicidally effective amounts to fungi and/or their habitats, such asvegetative hosts and non-vegetative hosts, e.g., animal products. Theamount used will, of course, depend on several factors such as the host,the type of fungus and the particular compound of the invention. As withmost pesticidal compounds, the fungicides of the invention are notusually applied full strength, but are generally incorporated withconventional, biologically inert extenders or carriers normally employedfor facilitating dispersion of active fungicidal compounds, recognizingthat the formulation and mode of application may affect the activity ofthe fungicide. Thus, the fungicides of the invention may be formulatedand applied as granules, as powdery dusts, as wettable powders, asemulsifiable concentrates, as solutions, or as any of several otherknown types of formulations, depending on the desired mode ofapplication.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersant. These compositionsnormally contain from about 5% to 80% fungicide, and the rest inertmaterial, which includes dispersing agents, emulsifying agents andwetting agents. The powder may be applied to the soil as a dry dust, orpreferably as a suspension in water. Typical carriers include fuller'searth, kaolin clays, silicas, and other highly absorbent, readilywettable, inorganic diluents. Typical wetting, dispersing or emulsifyingagents include, for example: the aryl and alkylaryl sulfonates and theirsodium salts; alkylamide sulfonates, including fatty methyl taurides;alkylaryl polyether alcohols, sulfated higher alcohols, and polyvinylalcohols; polyethylene oxides, sulfonated animal and vegetable oils;sulfonated petroleum oils, fatty acid esters of polyhydric alcohols andthe ethylene oxide addition products of such esters; and the additionproducts of long-chain mercaptans and ethylene oxide. Many other typesof useful surface-active agents are available in commerce. Thesurface-active agent, when used, normally comprises from 1% to 15% byweight of the fungicidal composition.

Dusts are freely flowing admixtures of the active fungicide with finelydivided solids such as talc, natural clays, kieselguhr, pyrophyllite,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, and other organic and inorganic solidswhich act as dispersants and carriers for the toxicant. These finelydivided solids have an average particle size of less than about 50microns. A typical dust formulation useful herein contains 75% silicaand 25% of the toxicant.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions which are readily dispersedin water or other dispersant, and may consist entirely of the fungicidewith a liquid or solid emulsifying agent, or may also contain a liquidcarrier such as xylene, heavy aromatic naphthas, isophorone, and othernonvolatile organic solvents. For application, these concentrates aredispersed in water or other liquid carrier, and are normally applied asa spray to the area to be treated.

Other useful formulations for fungicidal applications include simplesolutions of the active fungicide in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the fungicide is carried on relatively courseparticles, are of particular utility for aerial distribution or forpenetration of cover-crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier, suchas the Freons, may also be used. All of those techniques for formulatingand applying fungicides are well known in the art.

The percentages by weight of the fungicide may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprise 0.5% to 95% of the toxicant byweight of the fungicidal composition.

The fungicidal compositions may be formulated and applied with otheractive ingredients, including other fungicides, insecticides,nematocides, bactericides, plant-growth regulators, fertilizers, etc.

A further understanding of the invention can be had in the followingnon-limiting Examples. Wherein, unless expressly stated to the contrary,all temperatures and temperature ranges refer to the centrigrade systemand the term "ambient" or "room temperature" refers to about 20° to 25°C. The term "percent" refers to weight percent and the term "mol" or"mols" refers to gram mols. The term "equivalent" refers to a reagentequal in mols, to the mols of the preceding or succeeding reactantrecited in that example in terms of finite mols or finite weight orvolume. Unless expressly stated to the contrary, geometric isomer andracemic mixtures are used as starting materials and correspondinglyisomer mixtures are obtained as products. Also, unless expressly statedto the contrary, mixtures of E and Z isomers are generated wheneverpossible and are not separated.

Compounds which were prepared in accordance with Examples 1 to 5 beloware found in Table I.

EXAMPLE 1 Preparation of1-cyano-1-diethoxyphosphoro-2,2-bis(thio-3'-cis-chloroallyl)ethylene

To a suspension of 13.6 gm of pulverized potassium hydroxide in 150 mlof dioxane was added 17.7 gm of diethoxyphosphorocyanomethane over 1hour. Afterwards, 10 ml of carbon disulfide was added. The system wasstirred at room temperature for 18 hours and then the system was dilutedwith 150 ml of ether. The resulting precipitate was filtered and washedwith ether. The product was then suspended in 150 ml ofdimethylformamide. 27.7 gm of cis-1,3-dichloropropene was slowly addedto the system at from 0° to 10° C. The system was stirred at 50° C. for24 hours and the solution then poured into water. The product wasextracted with ethyl ether. The product was separated and purified bycolumn chromatography using silica gel and 20% ethyl acetate-hexane asthe eluant. The product was isolated and the solvent removed to give the1-cyano-1-diethoxyphosphoro-2,2-bis(thio-3'-chloroallyl)ethylene as abrown oil. Listed as Compound No. 1 in Table I.

EXAMPLE 2 Preparation of1-cyano-1-diethoxyphosphoro-2-thioallyl-2-(thio-3'-chloroallyl)ethylene

(a) 17.7 gm of ##STR10## in 30 ml of dimethylformamide is added dropwiseat 0° C. to a suspension of 6.7 gm of pulverized potassium hydroxide in150 ml of dimethylformamide. The mixture is stirred at this temperaturefor 30 minutes. Afterwards, 7.5 ml of carbon disulfide is slowly addedto the system. The system is warmed to room temperature and stirredthere for 3 hours. 12.2 gm of allyl bromide is then added to the system.The system is stirred at room temperature for 16 hours to give the1-cyano-1-diethoxyphosphoro-dithioacetic acid allyl ester.

(b) To the system containing the1-cyano-1-diethoxyphosphoro-dithioacetic acid allyl ester is added 6.7gm of pulverized potassium hydroxide at 0° C. The system is stirred for1/2 hour and then 11.6 gm of 1,3-dichloropropene is added. The system isstirred for 6 hours and then poured into water. The product is extractedwith ether and the ethereal extract first washed with sodium bicarbonatesolution and then with brine. The ethereal solution is then dried overmagnesium sulfate and the ether removed by stripping to give the crudeproduct. The product is separated and purified by chromatography to givethe title compound.

EXAMPLE 3 Preparation of1-ethoxycarbonyl-1-diethoxyphosphoro-2,2-bis(thio-2'-chloroallyl)ethylene

To a suspension of 6.8 gm of pulverized potassium hydroxide in 100 ml ofdioxane was added 11.2 gm of ##STR11## over 2 hours. Afterwards, 6 ml ofcarbon disulfide was added. The system was stirred at room temperaturefor 18 hours and then the system was diluted with 100 ml of ether. Theresulting precipitate was filtered and washed with ether. The productwas then suspended in 70 ml of dimethylformamide. 1,3-Dichloropropenewas slowly added to the system at from 0° to 10° C. The system wasstirred at 80° C. for 24 hours and the solution then poured into water.The product was extracted with ethyl acetate. The product was separatedand purified by column chromatography using silica gel and ethyl acetateas the elutant. The product was isolated and the solvent removed to givethe1-ethoxycarbonyl-1-diethoxyphosphoro-2,2-bis(thio-3'-chloroallyl)ethyleneas a yellow oil. Listed as Compound No. 9 in Table I.

EXAMPLE 4 Preparation of1-methoxycarbonyl-1-diethoxyphosphoro-2,2-bis[thio-(1'-methyl-2'-chloroallyl)]ethylene

To a suspension of 11.2 gm of pulverized potassium hydroxide in 200 mlof dioxane is added 21.0 gm of diethoxyphosphoroacetic acid methyl esterover 2 hours. Afterwards, 10 ml of carbon disulfide is added. The systemis stirred at room temperature for 16 hours and then the system isdiluted with 300 ml of ether. The resulting precipitate is filtered andwashed with water. The product is then suspended in 150 ml ofdimethylformamide. 25.0 gm of 2,3-dichlorobut-1-ene is slowly added tothe system at 0° C. to 10° C. The system is stirred for 16 hours and thesolution is then poured into water. The product is separated andpurified by column chromatography. The product is isolated and thesolvent removed to give the1-methoxycarbonyl-1-diethoxyphosphoro-2,2-bis[thio-(1'-methyl-2'-chloroallyl)]ethylene,##STR12##

EXAMPLE 5 Preparation of1-ethoxycarbonyl-1-diethoxythiophosphoro-2,2-bis(thio-2'-bromoallyl)ethylene

To a suspension of 12 gm of pulverized potassium hydroxide in 100 ml ofdioxane is added 24 gm of diethoxythiophosphoroacetic acid ethyl esterover 1 hour. Afterwards, 5 ml of carbon disulfide is added. The systemis stirred at room temperature for 16 hours and then the system isdiluted with 150 ml of ether. The resulting precipitate is filtered andwashed with ether. The product is then suspended in 150 ml ofdimethylformamide. 20.5 gm of 2,3-dibromopropene is slowly added to thesystem at from 0° to 10° C. The system is stirred at 80° C. for 24 hoursand the solution then poured into water. The product is extracted withether. The product is separated and purified by column chromatography.The product is isolated and the solvent removed to give the titlecompound.

Compounds which are prepared in accordance with Examples 1 to 5 aboveinclude, for instance:

1-cyano-1-diethoxyphosphoro-2,2-bis(thio-3'-chloroallyl)ethylene;

1-cyano-1-diethoxythiophosphoro-2,2-bis(thio-3'-chloroallyl)ethylene;

1-cyano-1-dimethoxyphosphoro-2-thioallyl-2-(thio-3'-chloroallyl)ethylene;

1-cyano-1-di-n-propoxyphosphoro-2-thioallyl-2-(thio-3'-bromoallyl)ethylene;

1-cyano-1-dimethoxythiophosphoro-2-thioallyl-2-(thio-3'-bromoallyl)ethylene;

1-cyano-1-dihexoxythiophosphoro-2,2-bis(thio-2'-bromoallyl)ethylene;

1-cyano-1-diethoxythiophosphoro-2,2-bis(thio-2',3'-dichloroallyl)ethylene;

1-methoxycarbonyl-1-diethoxyphosphoro-2,2-bis(thio-3'-chloroallyl)ethylene;

1-ethoxycarbonyl-1-diethoxythiophosphoro-2,2-bis(thio-3'-chloroallyl)ethylene;

1-n-propoxycarbonyl-1-dimethoxyphosphoro-2-thioallyl-2-(thio-3'-chloroallyl)ethylene;

1-ethoxycarbonyl-1-di-n-propoxyphosphoro-2-thioallyl-2-(thio-3'-bromoallyl)ethylene;

1-ethoxycarbonyl-1-dimethoxythiophosphoro-2-thioallyl-2-(thio-3'-bromoallyl)ethylene;and

1-ethoxycarbonyl-1-diethoxythiophosphoro-2,2-bis(thio-2'-bromoallyl)ethylene;

1-ethoxycarbonyl-1-diethoxyphosphoro-2,2-bis(thiopropargyl)ethylene.

EXAMPLE 6 Bean Powdery Mildew

The compounds of the invention were tested for the control of the BeanPowdery Mildew organism Erysiphe polygoni. Seedling bean plants weresprayed with a 250-ppm solution of the test compound in acetone, waterand a nonionic emulsifier. The sprayed plants were then inoculated 1 daylater with the organism. The plants were maintained for 10 days attemperatures of 68° F. at night with daytime temperatures of 72° to 80°F.; relative humidity was maintained at 40% to 60%. The percent diseasecontrol provided by a given test compound was based on the percentdisease reduction relative to the untreated check plants. The resultsare tabulated in Table II.

EXAMPLE 7 Tomato Late Blight

Compounds of the invention were tested for the preventative control ofthe Tomato Late Blight organism Phytophthora infestans. Five- tosix-week-old tomato (cultivar Bonny Best) seedlings were used. Thetomato plants were sprayed with a 250-ppm suspension of the testcompound in acetone, water and a nonionic emulsifier. The sprayed plantswere then inoculated 1 day later with the organism, placed in anenvironmental chamber and incubated at 66° to 68° F. and 100% relativehumidity for at least 16 hours. Following the incubation, the plantswere maintained in a greenhouse for approximately 7 days. The percentdisease control provided by a given test compound was based on thepercent disease reduction relative to untreated check plants. Theresults are tabulated in Table II.

EXAMPLE 8 Celery Late Blight

The Celery Late Blight tests were conducted using celery (Utah) plants11 weeks old. The Celery Late Blight organism was Septoria apii. Thecelery plants were sprayed with 250-ppm solutions of the candidatetoxicant mixed with acetone, water and a nonionic emulsifier. The plantswere then inoculated with the organism and placed in an environmentalchamber and incubated at 66° to 68° F. in 100% relative humidity for anextended period of time (approximately 48 hours). Following theincubation, the plants were allowed to dry and then were maintained in agreenhouse for approximately 14 days. The percent disease controlprovided by a given candidate toxicant is based on the percent diseasereduction relative to untreated check plants. The results are reportedin Table II.

EXAMPLE 9 Tomato Early Blight

Compounds of the invention were tested for the control of the TomatoEarly Blight organism Alternaria solani conidia. Tomato (variety BonnyBest) seedlings of 6- to 7-weeks old were used. The tomato plants weresprayed with a 250-ppm solution of the test compound in anacetone-and-water solution containing a small amount of a nonionicemulsifier. The sprayed plants were inoculated 1 day later with theorganism, placed in an environmental chamber and incubated at 66° to 68°F. and 100% relative humidity for 24 hours. Following the incubation,the plants were maintained in a greenhouse for about 12 days. Percentdisease control was based on the percent disease development onuntreated check plants. The compounds tested and the results aretabulated in Table II.

EXAMPLE 10 Grape Downy Mildew

The compounds of the invention were tested for the control of the GrapeDowny Mildew organism Plasmopara viticola. Detached leaves, between 70and 85 mm in diameter, 7-week-old Vitis vinifera cultivar Emperor grapeseedlings were used as hosts. The leaves were sprayed with a 250-ppmsolution of the test compound in acetone. The sprayed leaves were dried,inoculated with a spore suspension of the organism, placed in a humidenvironmental chamber and incubated at 66° to 68° F. and about 100%relative humidity. After incubation for 2 days, the plants were thenheld in a greenhouse 7 to 9 days; then the amount of disease control wasdetermined. The percent disease control provided by a given testcompound was based on the percent disease reduction relative tountreated check plants. The results are tabulated in Table II.

EXAMPLE 11 Leaf Rust

The Leaf Rust test was made using pinto beans. The pathogen was Uronycesphaseoli tipica. The pinto bean plants were sprayed with a 250-ppmsolution of the test compound in an acetone-water mixture containing anonionic emulsifier. The treated plants were inoculated thereafter withthe pathogen and then incubated in an environmental chamber forapproximately 20 hours at 100% relative humidity and a temperature of68° to 70° F. The plants were then removed from the chamber, allowed todry, and then maintained in a greenhouse at a 60% to 80% relativehumidity. The rate of infection on the leaves was made after about 14days. The percent disease control provided by a given test compound wasbased on the percent disease reduction relative to untreated checkplants. The results are reported in Table II.

EXAMPLE 12 Rice Blast

Compounds of this invention were tested for control of the Rice Blastorganism Piricularia oryzae, using 10- to 14-day-old rice plantseedlings (Calrose M-9 variety). Seedling plants were sprayed with a625-ppm solution of the test compound in acetone, water and a nonionicemulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1day later with the organism in an environmental chamber. Afterinoculation, the plants were kept in an environmental chamber for about48 hours under conditions of about 72° to 75° F. and about 100% relativehumidity. Following the incubation period, the plants were placed in agreenhouse with a temperature of about 72° F. and maintained with bottomwatering for about 12 to 16 days. The percent disease control providedby a given test compound is based on a comparison of the percentagedisease relative to the percent disease development on the untreatedcheck plants. ##EQU1## The results are tabulated in Table II.

                                      TABLE I                                     __________________________________________________________________________    COMPOUNDS OF THE FORMULA                                                       ##STR13##                                                                                          ANALYSIS                                                Compound              Carbon Hydrogen                                                                             Nitrogen                                  No.   R    R.sup.1    Calc.                                                                            Found                                                                             Calc.                                                                            Found                                                                             Calc.                                                                            Found                                                                             Form                               __________________________________________________________________________    1     CN                                                                                  ##STR14## 38.81                                                                            38.95                                                                             4.51                                                                             4.60                                                                              3.48                                                                             3.47                                                                              oil                                2     CN   CH.sub.2 CClCHCl                                                                         33.14                                                                            31.16                                                                             3.42                                                                             3.47                                                                              2.97                                                                             2.88                                                                              oil                                3     CN                                                                                  ##STR15## 38.81                                                                            38.93                                                                             4.51                                                                             4.41                                                                              3.48                                                                             3.43                                                                              oil                                4     CN                                                                                  ##STR16## 38.81                                                                            37.51                                                                             4.51                                                                             4.55                                                                              3.48                                                                             3.56                                                                              oil                                5     CN   CH.sub.2 CHCHCH.sub.3                                                                    49.84                                                                            49.74                                                                             6.69                                                                             6.92                                                                              3.88                                                                             3.77                                                                              oil                                       ##STR17##                                                                          ##STR18## 40.09                                                                            36.46                                                                             5.16                                                                             4.72       oil                                7                                                                                    ##STR19##                                                                          ##STR20## 40.09                                                                            36.92                                                                             5.16                                                                             4.68       oil                                8                                                                                    ##STR21##                                                                          ##STR22## 34.76                                                                            31.20                                                                             4.08                                                                             3.44       oil                                9                                                                                    ##STR23##                                                                          ##STR24## 40.09                                                                            36.06                                                                             5.16                                                                             4.53       oil                                10                                                                                   ##STR25##                                                                         CH.sub.2 CHCHCH.sub.3                                                                    49.98                                                                            46.90                                                                             7.10                                                                             5.80       oil                                __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                        FUNGICIDAL ACTIVITY                                                           ACTIVITY IN TERMS OF % CONTROL                                                Compound                                                                      No.     GDM     TLB     CLB   TEB  BR   BPM  RB                               ______________________________________                                        1       63      57      46    0    0    16   13                               2       98      64      50    21   0    0    --                               3       69      19      67    29   0    0    --                               4       78      50      33    0    0    0    28                               5       8       0       62    0    0    0    20                               6       11      32      0     23   0    0    --                               7       0       18      0     27   0    0    --                               8       11      0       13    14   0    0    --                               9       25      21      0     5    0    0    --                               10      6       25      0     11   0    0    --                               ______________________________________                                         GDM--Grape Downy Mildew (Plasmopara viticola)                                 TLB--Tomato Late Blight (Phytophthora infestans conidia)                      CLB--Celery Late Blight (Septoria apii)                                       TEB--Tomato Early Blight (Alternaria solani conidia)                          BR--Bean Rust Eradicant (Uronyces phaseoli tipica)                            BPM--Bean Powdery Mildew (Erysiphe polygoni)                                  RB--Rice Blast (Piricularia oryzae)                                      

What is claimed is:
 1. A compound having the formula: ##STR26## whereinR and R¹ are independently lower alkenyl or lower alkenyl substitutedwith 1 to 3 of the same or different halogens;R² and R³ areindependently hydrogen or lower alkyl; R⁴ and R⁵ are independently loweralkyl; R⁶ is cyano or --COOR⁷ wherein R⁷ is lower alkyl; and Y is oxygenor sulfur.
 2. A method for controlling fungi which comprises applying tothe fungus or its habitat a fungicidally effective amount of thecompound of the formula defined in claim
 1. 3. A compound of the formuladescribed in claim 1 wherein R² and R³ are hydrogen.
 4. A compound ofthe formula described in claim 3 wherein R and R¹ are lower alkenyl. 5.A compound of the formula described in claim 4 wherein R and R¹ arevinyl.
 6. A compound of the formula described in claim 3 wherein R andR¹ are lower alkenyl substituted with 1 to 3 of the same or differenthalogens.
 7. A compound of the formula described in claim 6 wherein Rand R¹ are vinyl substituted with 1 or 2 chloro groups.
 8. A compound ofthe formula described in claim 3 wherein R⁴ and R⁵ are ethyl.
 9. Acompound of the formula described in claim 8 wherein Y is oxygen.
 10. Acompound of the formula described in claim 9 wherein R⁶ is cyano.
 11. Acompound of the formula described in claim 9 wheein R⁶ is ##STR27##wherein R⁷ is lower alkyl.
 12. A compound of the formula described inclaim 11 wherein R⁷ is ethyl.
 13. A compound of the formula described inclaim 10 wherein R and R¹ are both --CCl═CHCl.
 14. A compound of theformula described in claim 12 wherein R and R¹ are both --CH═CHCl.
 15. Afungicidal composition comprising a biologically inert carrier and afungicidally effective amount of the compound defined in claim 1.